Rapid Dihydrogen Cleavage by Persistent Nitroxide Radicals under Frustrated Lewis Pair Conditions

被引：24

作者：

Tao, Xin ^{[1
]}

Kehr, Gerald ^{[1
]}

Wang, Xiaowu ^{[1
]}

Daniliuc, Constantin G. ^{[1
]}

Grimme, Stefan ^{[2
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Organ Chem Inst, Corrensstr 40, D-48149 Munster, Germany

[2] Univ Bonn, Mulliken Ctr Theoret Chem, Inst Phys & Theoret Chem, Beringstr 4, D-53115 Bonn, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 28期

基金：

欧洲研究理事会;

关键词：

boron; dihydrogen splitting; frustrated Lewis pair; persistent radical; radical reactions; HYDROGEN-ATOM REACTIONS; PERFLUOROPHENYL DERIVATIVES; CARBON-MONOXIDE; KINETICS; TEMPO; ACTIVATION; CHEMISTRY; MECHANISM; ACID; REACTIVITY;

D O I：

10.1002/chem.201602058

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Persistent radicals undergo hydrogen atom abstraction reactions with a great variety of substrates, but not with dihydrogen. It has now been found that the TEMPO radical splits dihydrogen under mild conditions in the presence of the strong bulky B(C6F5)(3) boron Lewis acid. The reaction is thought to proceed by a typical frustrated Lewis pair mechanism with the TEMPO radical acting as the active Lewis base. The reaction was analyzed by DFT, which indicates that no significant spin density on the hydrogen atoms is accumulated along the H-2 splitting reaction path.

引用

页码：9504 / 9507

页数：4